Water-soluble polyhydroxyaminoether and process for preparing the same

ABSTRACT

A water soluble polymer comprising a copolyhydroxyaminoether having side-chains of polyalkylene oxides, an aqueous solution of said polymer and process for preparing the copolyhydroxyaminoether.

BACKGROUND OF THE INVENTION

This invention relates to water-soluble polymers. Water-soluble polymersare used in many applications ranging from improved oil recovery, metalworking fluid lubrication, and gellants in the food industry. It isknown that the production of large amounts of water from oil and gaswells constitutes one of the major expenses in the overall recovery ofhydrocarbons from a subterranean reservoir and that some water-solublepolymers reduce such water production. See, for example, Treybig et al.U.S. Pat. No. 6,569,983 and Ahmed et al. U.S. Pat. No. 6,051,670.

It is also well known that polymers and gelled or crosslinkedwater-soluble polymers have been used to alter the permeability ofsubterranean formations in order to enhance the effectiveness of waterflooding operations. Generally, the polymers are injected into theformation and permeate into the regions having the highest waterpermeability. It is theorized that the polymer blocks the waterpermeable zones in the formation, thus reducing the amount of waterproduced with the oil. Existing polymers, such as polyacrylamides, doreduce water production but they also reduce oil production.

It would be desirable to provide water-soluble polymers that reducewater production but does not affect oil production.

SUMMARY OF THE INVENTION

In a first aspect, the present invention is a water-soluble polymercomprising a copolyhydroxyaminoether having side-chains of polyalkyleneoxides.

In a second aspect, the present invention is a composition comprising anaqueous fluid and the water-soluble polymer of the first aspect.

In a third aspect, the present invention is a process for preparing thewater soluble polymer of the first aspect which comprises reacting (1) aprimary amine, a bis(secondary) diamine, or a mono-amine-functionalizedpoly(alkylene oxide) or mixtures thereof with (2) a diglycidyl ether, adiepoxy-functionalized poly(alkylene oxides) or mixtures thereof underconditions sufficient to cause the amine moieties to react with theepoxy moieties to form a polymer backbone having amine linkages, etherlinkages and pendant hydroxyl moieties.

In a fourth aspect, the present invention is a process for preparing thewater soluble polymer of the first aspect which comprises reacting anequivalent or excess of a difunctional amine or mixtures thereof with anexcess or equivalent amount of a diglycidyl ether of a bisphenol ormixtures thereof, optionally in the presence of a monofunctionalnucleophile which functions as a terminating agent and, optionally, inthe presence of a catalyst and/or a solvent.

In a fifth aspect, the present invention is a process for preparing thewater soluble polymer of the first aspect which comprises dissolving inan organic or non-organic solvent an amine selected from the groupconsisting of primary amine, a bis(secondary) diamine, or amono-amine-functionalized poly(alkylene oxide) or mixtures thereof,adding to the amine solution an epoxide selected from the groupconsisting of a diglycidyl ether, a diepoxy-functionalized poly(alkyleneoxides) or mixtures thereof in an amine hydrogen equivalent to epoxideequivalent ratio of from 1.01:1 to 1.1:1 under conditions sufficient tocause the amine moieties to react with the epoxy moieties to form apolymer backbone having amine linkages, ether linkages and pendanthydroxyl moieties.

Other aspects of the present invention will become apparent from thefollowing detailed description and claims.

DETAILED DESCRIPTION OF THE INVENTION

Preferably, the copolyhydroxyaminoether is represented by the formula:

wherein R is hydrogen or alkyl; R¹ is an aromatic or substitutedaromatic moiety; Y is an organic moiety that does not contain an epoxygroup and Z is an organic moiety, optionally containing an epoxy group;x is 0-0.99; and n is 5-400; each A is individually an amino grouprepresented by one of the formulas:

wherein R² is hydrocarbyl or substituted hydrocarbyl; R³ is C₂-C₁₀hydrocarbylene or substituted hydrocarbylene; R⁴ is C₂-C₂₀hydrocarbylene or substituted hydrocarbylene, wherein the substituent(s)is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido,alkylcarbonyl, or arylcarbonyl; and each B is represented by theformula:

wherein R⁵ is hydrocarbyl; R⁶ is hydrogen, methyl, ethyl, hydrocarbyl,or mixtures thereof; and x is 0-0.99 when q is greater than 40; but lessthan 0.2 or greater than 0.8 when q is less than 40.

For purposes of this invention, the term “hydrocarbyl” means amonovalent hydrocarbon such as alkyl, cycloalkyl, aralkyl, or aryl andthe term “hydrocarbylene” means a divalent hydrocarbon such as alkylene,cycloalkylene, aralkylene or arylene.

In the more preferred embodiment of this invention, R is hydrogen; R¹ isisopropylidenediphenylene, 1,4-phenylene, 1,3-phenylene,methylenediphenylene, thidodiphenylene, carbonyldiphenylene, orcombinations thereof; R² is methyl, ethyl, phenyl, benzyl,2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2,3-dihydroxypropyl,2-(acetamido)ethyl, or combinations thereof; R³ and R⁴ are independentlyethylene, 1,2-propylene, 1,2-butylene, or combinations thereof; and R⁵is C₁-C₂₀ alkyl.

In the most preferred embodiment of this invention, R¹ isisopropylidenediphenylene, R² is 2-hydroxyethyl; R⁵ is hydrogen, methyl,ethyl, propyl, butyl, benzyl or combinations thereof; R⁶ is a mixture ofhydrogen and methyl; Y and Z are N-(2-hydroxyethyl)piperazinyl orbis(2-hydroxyethyl)amino, q is 20-50, and n is 10-25.

The water-soluble polymer can be recovered from the reaction mixture byconventional methods. For example, the reaction mixture containing thepolymer and optional solvent can be diluted with a suitable solvent suchas dimethylformamide, cooled to room temperature, and the polymerisolated by precipitation into a non-solvent. The precipitated polymercan then be purified by washing or multiple washings by the non-solvent.The polymer is collected by filtration, washed with a suitablenon-solvent and then dried. The water-soluble polymer can also berecovered from solution by volatilization of the solvent by combinationof temperature and vacuum.

The difunctional amines which can be employed in the practice of thepresent invention include the bis-secondary amines and primary amines.

The primary amines which can be employed in the practice of the presentinvention to prepare the polymers include aniline and substitutedanilines, e.g., 4-(methylamido)aniline, 4-methylaniline,4-methoxy-aniline, 4-tert-butylaniline, 3,4-dimethoxyaniline,3,4-dimethylaniline; alkylamines, and substituted alkyl amines, e.g.,butylamine and benzylamine; and alkanol amines; e.g., 2-aminoethanol and1-aminopropan-2-ol. Preferred primary amines are aniline,4-methoxyaniline, 4-tert-butylaniline, butylamine, and 2-aminoethanol.The most preferred primary amine is 2-aminoethanol.

The bis-secondary amines which can be employed in the practice of thepresent invention to prepare the polymers include piperazine andsubstituted piperazines, e.g., dimethylpiperazine and2-methylamidopiperazine; bis(N-methylamino)benzene,1,2-bis(N-methylamino)ethane, andN,N′-bis(2-hydroxyethyl)ethylenediamine. Preferred bis-secondary aminesare piperazine, dimethylpiperazine, and 1,2-bis(N-methylamino)ethane.The most preferred bis-secondary amine is piperazine.

The amine-functionalized poly(alkylene oxides) which can be employed inthe practice of the present invention to prepare the polymers includethose materials represented by the general formula:

wherein R⁶ is hydrogen, methyl, ethyl, hydrocarbyl or mixtures thereof;R₅ is hydrocarbyl and q is from about 1 to about 1000. Typical of aminesof this class are the “M” series Jeffamine™ products manufactured byHuntsman. They are typically prepared by polymerizing ethylene oxide,propylene oxide, butylene oxide, and the like or mixtures thereof withaliphatic alcohol initiators and then subsequently converting theresulting terminal hydroxyl group to an amine moiety.

Epoxy-functionalized poly(alkylene oxides) can be employed also in thepractice of the present invention to prepare the polymers, and they canbe mixed with diglycidyl ethers of bisphenols. Suitableepoxy-functionalized poly(alkylene oxides) are those represented by thegeneral formula:

wherein R₁ is hydrogen, methyl, or mixtures thereof; and y is from about1 to about 40. Typical of epoxides of this class are the “700” seriesD.E.R.™ epoxy resins manufactured by The Dow Chemical Company. They aresynthesized by polymerizing ethylene oxide, propylene oxide, or mixturesthereof with hydroxide initiators and then reacting the resultingpoly(alkylene oxide) diol with epichlorohydrin.

The diglycidyl ethers which can be employed in the practice of thepresent invention for preparing the polymers include9,9-bis(4-hydroxyphenyl)fluorene, 4,4′-methylene bisphenol (bisphenolF), hydroquinone, resorcinol, 4,4′-sulfonyldiphenol, 4,4′-thiodiphenol,4,4′-oxydiphenol, 4,4′-dihydroxybenzophenone,tetrabromoisopropylidenebisphenol, dihydroxydinitrofluorenylidenediphenylene, 4,4′-biphenol,4,4′-dihydroxybiphenylene oxide, bis(4-hydroxyphenyl)methane,.alpha.,.alpha.-bis(4-hydroxyphenyl)ethylbenzene,2,6-dihydroxynaphthalene and 4,4′-isopropylidene bisphenol (bisphenol A)and the diglycidyl ethers of the amide-containing bisphenols such asN,N′-bis(hydroxyphenyl)alkylenedicarboxamides,N,N′-bis(hydroxyphenyl)arylenedicarboxamides,bis(hydroxybenzamido)alkanes or bis(hydroxybenzamido)arenes,N-(hydroxyphenyl)hydroxybenzamides, 2,2-bis(hydroxyphenyl)acetamides,N,N′-bis(3-hydroxyphenyl)glutaramide, N,N′-bis(3-hydroxyphenyl)adipamide, 1,2-bis(4-hydroxybenzamido)ethane,1,3-bis(4-hydroxybenzamide)benzene,N-(4-hydroxyphenyl)-4-hydroxybenzamide, and2,2-bis(4-hydroxyphenyl)-acetamide. The more preferred diglycidyl ethersare the diglycidyl ethers of 9,9-bis(4-hydroxyphenyl)fluorene,hydroquinone, resorcinol, 4,4′-sulfonyldiphenol, 4,4′-thiodiphenol,4,4′-oxydiphenol, 4,4′-dihydroxybenzophenone, bisphenol F,tetrabromoisopropylidenebisphenol, dihydroxydinitrofluorenylidenediphenylene, 4,4′-biphenol,4,4′-dihydroxybiphenylene oxide, bis(4-hydroxyphenyl)methane,.alpha.,.alpha.-bis(4-hydroxyphenyl)ethyl-benzene,2,6-dihydroxynaphthalene and 4,4′-isopropylidene bisphenol (bisphenolA). The most preferred diglycidyl ethers are the diglycidyl ethers of4,4′-isopropylidene bisphenol (bisphenol A), 4,4′-sulfonyldiphenol,4,4′-oxydiphenol, 4,4′-dihydroxybenzophenone,9,9-bis(4-hydroxy-phenyl)fluorene and bisphenol F.

The monofunctional nucleophiles which function as terminating agentswhich can be employed in the practice of the present invention includesecondary amines, hydrogen sulfide, ammonia, ammonium hydroxide, ahydroxyarene, an aryloxide salt, a carboxylic acid, a carboxylic acidsalt, a mercaptan or a thiolate salt. Preferably, the hydroxyarene isphenol, cresol, methoxyphenol, or 4-tert-butylphenol; the aryloxide saltis sodium or potassium phenate; the carboxylic acid is acetic acid orbenzoic acid; the carboxylic acid salt is sodium acetate, sodiumbenzoate, sodium ethylhexanoate, potassium acetate, potassium benzoate,potassium ethylhexanoate, or calcium ethylhexanoate; the mercaptan is3-mercapto-1,2-propanediol or benzenethiol; and the thiolate salt issodium or potassium benzenethiolate.

Preferred catalysts include metal hydroxides, quaternary ammonium saltsor quaternary phosphonium salts. Especially preferred catalysts includesodium hydroxide, potassium hydroxide, ammonium hydroxide,ethyltriphenylphosphonium acetate, tetrabutylammonium bromide andbis(triphenylphosphoranylidene)ammonium chloride.

The conditions at which the reaction is most advantageously conductedare dependent on a variety of factors, including the specific reactants,solvent, and catalyst employed but, in general, the reaction isconducted under a non-oxidizing atmosphere such as a blanket ofnitrogen, preferably at a temperature from about 40° C. to about 190°C., more preferably at a temperature from about 50° C. to about 150° C.The reaction can be conducted neat (without solvent or other diluents).However in some cases, in order to ensure homogeneous reaction mixturesat such temperatures, it can be desirable to use inert organic solventsor water as solvent for the reactants. Examples of suitable solventsinclude dipropylene glycol methyl ether, available commercially asDowanol™ DPM, a product of The Dow Chemical Company, and the ethers orhydroxy ethers such as diglyme, triglyme, diethylene glycol ethyl ether,diethylene glycol methyl ether, dipropylene glycol methyl ether,propylene glycol phenyl ether, propylene glycol methyl ether andtripropylene glycol methyl ether as well as aprotic amide solvents like1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, and mixtures thereof.

It is most preferred that the polyalkylene oxide chain be rich inethylene oxide relative to propylene oxide. The length of thepolyalkylene side-chain can be from 1 alkylene oxide units to 1000alkylene oxide units, preferably from 2 alkylene oxide units to 500alkylene oxide units, more preferably from 5 alkylene oxide units to 250alkylene oxide units and, most preferably, from 10 alkylene oxide unitsto 100 alkylene oxide units.

Preferably, the copolyhydroxyaminoether has a molecular weight of fromabout 1000 to about 500,000, more preferably from about 2000 to about250,000 and, most preferably, from about 5000 to about 100,000. Thecopolymer molecular weight can be controlled by either off-stoichiometryof the N—H to epoxy ratio or by introduction of monofunctionalterminating agents, described previously, at the start of thepolymerization process or added during or at the end of thepolymerization process.

Advantageously, the polyalkylene oxide containing polymer repeat unitsis used in an amount of from about 1 to about 99 mole %, morepreferably, in an amount of from about 1 to about 25 mole %.

Preferably, the copolyhydroxyaminoethers have glass transitiontemperatures of from about (−)60° C. to about 150° C.

Aqueous solutions of copolyhydroxyaminoethers can exhibit a cloud pointor lower critical solution temperature (LCST), such that an aqueoussolution of copolyhydroxyaminoethers flow at some temperature below theboiling point of water, preferably room temperature, and becomes moreviscous and/or gels with the possible optical transition fromclear-to-hazy/opaque/turbid at more elevated temperatures. The termcloud point is a term that can be used to describe the opticaltransition. As used herein, the term “LCST” describes the temperature atwhich the polymer solution experiences a phase transition going from onephase (homogeneous solution) to at least a two-phase system (a polymerrich phase and a more solvent rich phase) as the solution temperatureincreases. The cloud point or LCST can be changed by the addition ofsalts, acids, or bases to the aqueous solutions ofpolyhydroxyaminoethers. The cloud point or LCST can also be changed as afunction of concentration of polyhydroxyaminoether in aqueous solutionsas well as the molecular weight of the polyhydroxyaminoether.

The following working examples are given to illustrate the invention andshould not be construed as limiting its scope. Unless otherwiseindicated, all parts and percentages are by weight.

The following materials are used in the Examples:

-   -   D.E.R.™ 332 A high purity bisphenol A diglycidyl ether        manufactured by THE DOW CHEMICAL COMPANY.    -   JEFFAMINE™ XTJ506 A polyoxyalkylenemonoamine with a propylene        oxide/ethylene oxide ratio of ˜3/19 and a molecular weight of        ˜1000 manufactured by Huntsman.    -   JEFFAMINE™ M2070 A polyoxyalkylenemonoamine with a propylene        oxide/ethylene oxide ratio of ˜10/32 and a molecular weight of        2000 and manufactured by Huntsman.

EXAMPLE 1 Solution, D.E.R. 332/MEA/JEFFAMINE XTJ506, 100/80/20 (m/m/m),DP˜15, hydroxyethylpiperazine)

Into a 1 L resin kettle is loaded D.E.R. 332 (180.00 grams, EEW 171),JEFFAMINE XTJ 506 (101.75 grams, Mn ˜1030), ethanolamine (24.10 grams),1-(2-hydroxethyl)piperazine (8.60 grams), and N,N-dimethylacetamide,anhydrous (250 mL). Stirred reaction mixture under positive nitrogen isinitially warmed to ˜45° C. When initial exotherm subsides, reactionsetpoint is raised to 75° C. and after temperature rise stabilizes,setpoint is raised to 140° C. and held at that temperature for ˜1 hour.Reaction mixture is cooled with N,N-dimethylacetamide subsequentlyremoved under vacuum at ˜95° C. Product has an inherent viscosity of0.18 dL/g (N,N-dimethylformamide, 30.0° C., 0.5 g/dL). Half-height glasstransition by DSC at 10° C./min heating rate is 6° C. A 20 wt % solutionof the product in water is prepared that is of low viscosity andessentially clear at room temperature; at ˜50° C. the solution becomestranslucent/opaque white and a soft-gel of high viscosity; when solutionis cooled to room temperature it once again becomes of low viscosity andessentially clear.

EXAMPLE 2 Solution, D.E.R. 332/MEA/JEFFAMINE XTJ506, 100/85/15 (m/m/m),DP-25, hydroxyethylpiperazine

Into a 1 L resin kettle is loaded D.E.R. 332 (76.00 grams, EEW 171),JEFFAMINE XTJ 506 (35.59 grams, Mn ˜1031), ethanolamine (10.93 grams),1-(2-hydroxethyl)piperazine (2.28 grams), and N,N-dimethylacetamide,anhydrous (150 mL). Stirred reaction mixture under positive nitrogen isinitially warmed to ˜45° C. When initial exotherm subsides, reactionsetpoint is raised to 75° C. and after temperature rise stabilizes,setpoint is raised to 100° C. for less than ½ hour, setpoint raised to140° C. and held at that temperature for ˜1.25 hour. Reaction mixture iscooled with N,N-dimethylacetamide subsequently removed under vacuum at˜95° C. Product has an inherent viscosity of 0.23 dL/g(N,N-dimethylformamide, 30.0° C., 0.5 g/dL). Half-height glasstransition by DSC at 10° C./min heating rate is 13° C. A 15 wt %solution of the product in water is prepared at room temperature that at˜50° C. becomes a translucent, white gel.

EXAMPLE 3 Solution, D.E.R. 332/MEA/JEFFAMINE XTJ506, 100/85/15 (m/m/m)

Into a 100 mL resin kettle is loaded D.E.R. 332 (12.000 grams, EEW 171),Jeffamine XTJ 506 (5.426 grams, Mn ˜1031), ethanolamine (1.822 grams),and N,N-dimethylacetamide, anhydrous (25 mL). Stirred reaction mixtureunder positive nitrogen is initially warmed to ˜45° C. When initialexotherm subsides, reaction setpoint is raised to 75° C. and aftertemperature rise stabilizes, setpoint is raised to 100° C. for less than¾ hour, setpoint raised to 140° C. and held at that temperature for˜3.25 hour. Reaction mixture is held at 100° C. overnight. Ethanolamine(0.026 g) in N,N-dimethylacetamide (2 mL) is added to kettle and after30 minutes at 100° C., temperature is raised to 140° C. for ˜2 hourswith subsequent cooling. N,N-dimethylacetamide is subsequently removedunder vacuum at ˜95° C. Product has an inherent viscosity of 0.33 dL/g(N,N-dimethylformamide, 30.0° C., 0.5 g/dL). Half-height glasstransition by DSC at 10° C./min heating rate is 16° C. No terminator isused in the reaction. A 20 wt % solution of the product in water isprepared.

EXAMPLE 4 Solution, D.E.R. 332/MEA/JEFFAMINE XTJ506, 100/88.75/11.25(m/m/m)

Into a 100 mL resin kettle is loaded D.E.R. 332 (13.000 grams, EEW 171),Jeffamine XTJ 506 (4.409 grams, Mn ˜1031), ethanolamine (2.061 grams),and N,N-dimethylacetamide, anhydrous (25 mL). Stirred reaction mixtureunder positive nitrogen is initially warmed to ˜45° C. When initialexotherm subsides, reaction setpoint is raised to 75° C. and aftertemperature rise stabilizes, setpoint is raised to 100° C. for less than˜½ hour, setpoint raised to 140° C. and held at that temperature for ˜3hour. Reaction mixture is held at 100° C. overnight. Ethanolamine (0.022g) in N,N-dimethylacetamide (2 mL) is added to kettle and temperature israised to 140° C. for ˜1.5 hours. Product is precipitated in ice-water,water washed, and dried at ˜55° C. in a vacuum oven. Product has aninherent viscosity of 0.34 dL/g (N,N-dimethylformamide, 30.0° C., 0.5g/dL). Half-height glass transition by DSC at 10° C./min heating rate is31° C. No terminator is used in the reaction. The polymer produced isnot water soluble.

EXAMPLE 5 Solution, D.E.R. 332/MEA/Jeffamine XTJ506, 100/92.5/7.5(m/m/m))

Into a 100 mL resin kettle is loaded D.E.R. 332 (14.000 grams, EEW 171),Jeffamine XTJ 506 (3.165 grams, Mn ˜1031), ethanolamine (2.313 grams),and N,N-dimethylacetamide, anhydrous (25 mL). Stirred reaction mixtureunder positive nitrogen is initially warmed to ˜45° C. When initialexotherm subsides, reaction setpoint is raised to 75° C. and aftertemperature rise stabilizes, setpoint is raised to 100° C. for ˜1 hour,setpoint raised to 140° C. and held at that temperature for ˜3.25 hour.Reaction mixture is held at 100° C. overnight. Ethanolamine (0.022 g) inN,N-dimethylacetamide (2 mL) is added to kettle and temperature israised to 140° C. for ˜1 hours with subsequent addition ofN,N-dimethylacetamide (10 mL) and cooling. Product is precipitated inice water, water washed, and dried under vacuum at ˜55° C. Product hasan inherent viscosity of 0.46 dL/g (N,N-dimethylformamide, 30.0° C., 0.5g/dL). Half-height glass transition by DSC at 10° C./min heating rate is46° C. No terminator is used in the reaction. The polymer produced isnot water soluble.

EXAMPLE 6 MELT, D.E.R. 332/MEA/Jeffamine XTJ506 100/80/20 (m/m/m) DP˜15, hydroxyethylpiperazine

Into a 1L resin kettle is loaded D.E.R. 332 (345.15 g, EEW 172.7),Jeffamine XTJ 506 (189.24 g, Mn ˜1010), ethanolamine (45.78 g), and1-(2-hydroxyethyl)piperazine (16.27 g). Initial setpoint for the stirredreaction is 45° C. under positive N₂. Reaction mixture startsself-heating with cooling applied with temperature kept below ˜140-150°C. After temperature rise subsides, reaction is kept at 140° C. for 30minutes with product then cooled to room temperature. Product has aninherent viscosity of 0.19 dL/g (N,N-dimethylformamide, 30.0° C., 0.5g/dL) . Half-height glass transition by DSC at 10° C./min heating rateis 6° C. An aqueous solution of product is prepared by adding 312.5grams in portions to a stirred 2 L resin kettle containing water (1193.1g) and acetic acid (1.37 g) at ˜40° C. Aqueous sodium hydroxide (45.5mL, 0.50 N) is subsequently added to the solution with a 10 mL waterrinse.

EXAMPLE 7 MELT, D.E.R. 332/MEA/JEFFAMINE M2070 100/87.5/12.5 (m/m/m) DP˜13.7, diethanolamine

Into a 1L resin kettle is loaded D.E.R. 332 (317.97 g, EEW 172.7),JEFFAMINE M2070 (223.39 g, Mn ˜2083), ethanolamine (45.86 g), anddiethanolamine (13.15 g). Initial setpoint for the stirred reaction is45° C. under positive N₂. Reaction mixture starts self-heating withcooling applied with temperature kept below ˜140-150° C. Aftertemperature rise subsides, reaction is kept at 140° C. for 30 minuteswith product then cooled to room temperature. Product has an inherentviscosity of 0.17 dL/g (N,N-dimethylformamide, 30.0° C., 0.5 g/dL).Half-height glass transition by DSC at 10° C./min heating rate is 2° C.An aqueous solution of product is prepared by adding 312.5 grams inportions to a stirred 2 L resin kettle containing water (1193.1 g) andacetic acid (1.37 g) at ˜40° C. Aqueous sodium hydroxide (45.5 mL, 0.50N) is subsequently added to the solution with a 10 mL water rinse.

EXAMPLE 8 Solution, D.E.R. 332/MEA/JEFFAMINE M2070, 100/85/15 (M/M/M)

Into a 100 mL resin kettle is loaded D.E.R. 332 (10.000 grams, EEW 171),JEFFAMINE M2070 (8.932 grams, Mn ˜2083), ethanolamine (1.484 grams), andN-methylpyrrolidinone, anhydrous (20 mL). Stirred reaction mixture underpositive nitrogen is initially warmed to ˜45° C. When initial exothermsubsides, reaction setpoint is raised to 75° C. and after temperaturerise stabilizes, setpoint is raised to 100° C. for ˜2 hours, setpointraised to 140° C. and held at that temperature for ˜3.25 hour. Reactionmixture is held at 100° C. overnight. Ethanolamine (0.026 g) inN,N-dimethylacetamide (2 mL) is added to kettle and after 30 minutes at100° C., temperature is raised to 140° C. for ˜3.75 hours withsubsequent cooling to 100° C. overnight. Ethanolamine (0.017 g) in 2 mLN-methylpyrrolidinone is added to kettle with temperature raised to 140°C. for ˜4.25 hours and cooled. Product does not precipitate in water.Product precipitate in cold isopropanol and is washed with cold andambient isopropanol with product dried at ˜110° C. under vacuum. Producthas an inherent viscosity of 0.75 dL/g (N,N-dimethylformamide, 30.0° C.,0.5 g/dL). Half-height glass transition by DSC at 10° C./min heatingrate is ˜15° C. No terminator is used in the reaction.

EXAMPLE 9 Water Polymerization, D.E.R. 332/MEA/JEFFAMINE M-2070 and DEA

Into a 30 gal stainless steel reactor is loaded 8137.5 g water andmixing started at 100 RPM's. JEFFAMINE M-2070 (6437.1 g, Mn ˜1040),ethanolamine (1321.5 g) and diethanolamine (378.9 g) are added thenheated to 54-63° C. temperature. Pressure was 19.1-21.7 PSIA and mixingincreased to 200 RPM's. D.E.R. 332 (9084 g, EEW 172.7) was added over atime period of 1 hour and 48 minutes via a 2 gal stainless steel (SS316) charge pot. The reaction mixture was digested for 34 minutes andthen water (133.8 lbs) was added over a 31 minute time. The resultingsolution was mixed for 1 hr and 39 minutes then cooled to 25° C. andfiltered via a 25 micro Nomex bag filter system into polyethylenecontainers.

EXAMPLE 10 Dowanol PM Polymerization, D.E.R. 332/MEA/JEFFAMINE M-2070and DEA

Into a 30 gal stainless steel (SS 316) reactor is loaded 8137.5 g ofDowanol PM and mixing started at 100 RPM's. JEFFAMINE M-2070 (6437.1 g,Mn ˜1040), ethanolamine (1321.5 g) and diethanolamine (378.9 g) areadded then heated to 87-91.6° C. temperature. Pressure was 19.1-21.7PSIA and mixing increased to 200 RPM's. D.E.R 332 (9082 g, EEW 172.7)was added over a time period of 1 hour and 34 minutes via a 2 galstainless steel charge pot. The reaction mixture was digested for 2 hrand 43 minutes at a temperature of 89-101° C. and then water (133.7 lbs)was added over a 36 minute time. The resulting solution was mixed for 1hr at 67.1-89° C. and 150 RPM's then cooled to 26° C. and filtered via a25 micro Nomex bag filter system into polyethylene containers.

1. A water-soluble polymer comprising a copolyhydroxyaminoether havingside-chains of polyalkylene oxides.
 2. The polymer of claim 1represented by the formula:

wherein R is hydrogen or C₁-C₂₀ alkyl; R¹ is individually an aromatic orsubstituted aromatic moiety; Y is an organic moiety that does notcontain an epoxy group and Z is an organic moiety, optionally containingan epoxy group; x is 0-0.99; and n is 5-400; each A is individually anamino group represented by one of the formulas:

wherein R² is hydrocarbyl or substituted hydrocarbyl; R³ is C₂-C₁₀hydrocarbylene or substituted hydrocarbylene; R⁴ is C₂-C₂₀hydrocarbylene or substituted hydrocarbylene, wherein the substituent(s)is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido,alkylcarbonyl, or arylcarbonyl; and each B is represented by theformula:

wherein R⁵ is hydrocarbyl; each R⁶ is individually hydrogen, methyl,ethyl, hydrocarbyl or combinations (change made for consistency)thereof; and x is 0-0.99 when q is greater than 40 but less than 0.2 orgreater than 0.8 when q is less than
 40. 3. The polymer of claim 2wherein R is hydrogen; each R¹ is individuallyisopropylidenediphenylene, 1,4-phenylene, 1,3-phenylene,methylenediphenylene, thidodiphenylene, carbonyldiphenylene, orcombinations thereof; each R² is individually methyl, ethyl, phenyl,benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl,2,3-dihydroxypropyl, 2-(acetamido)ethyl, or combinations thereof; R³ andR⁴ are individually (change made for consistency) ethylene,1,2-propylene, 1,2-butylene, or combinations thereof; and R⁵ is C₁-C₂₀alkyl; R⁶ is a mixture of hydrogen and methyl; each of Y and Z areindividually bis(2-hydroxyethyl)amino or N-(2-hydroxyethyl)piperazinyl;q is 20-50, and n is 10-25.
 4. The polymer of claim 3 wherein R¹ isisopropylidenediphenylene and R² is 2-hydroxyethyl.
 5. The polymer ofclaim 3 wherein each R⁵ is individually hydrogen, methyl, ethyl, propyl,butyl, benzyl or combinations thereof; Y and Z arebis(2-hydroxyethyl)amino.
 6. A process for preparing a water-solublepolymer which comprises (1) reacting an equivalent or excess of adifunctional amine or mixtures thereof with an excess or equivalentamount of a diglycidyl ether of a bisphenol or mixtures thereof,optionally in the presence of a monofunctional nucleophile andoptionally in the presence of a catalyst and/or a solvent; or (2)reacting an equivalent or excess of a difunctional amine or mixturesthereof with an excess or equivalent amount of a diglycidyl ether of abisphenol or mixtures thereof, optionally in the presence of amonofunctional nucleophile which functions as a terminating agent and,optionally, in the presence of a catalyst and/or a solvent; or (3)dissolving in an organic or non-organic solvent an amine selected fromthe group consisting of primary amine, a bis(secondary) diamine, or amono-amine-functionalized poly(alkylene oxide) or mixtures thereof,adding to the amine solution a diglycidyl ether in an amine hydrogenequivalent to epoxide equivalent ratio of from 0.9:1 to 1.2:1 underconditions sufficient to cause the amine moieties to react with theepoxy moieties to form a polymer backbone having amine linkages, etherlinkages and pendant hydroxyl moieties.
 7. The process of claim 6wherein the non-organic solvent is water and the monofunctionalnucleophile is selected from the group consisting of a secondary amine,hydrogen sulfide, ammonia, ammonium hydroxide, a monofunctional phenol,an aryloxide salt, a carboxylic acid, a carboxylic acid salt, amercaptan, and thiolate salt.
 8. The process of claim 6 wherein thedifunctional amine is ethanolamine or a primary amine having theformula:

wherein R⁵, R⁶ and q are as defined above; the diglycidyl ether of abisphenol is the diglycidyl ether of bisphenol A.
 9. The process ofclaim 6 wherein the monofunctional nucleophile is selected from thegroup consisting of diethanolamine, N-(2-hydroxyethyl)piperazine,piperadine, diethylamine, dipropylamine, and dibenzylamine.
 10. Theprocess-of claim 6 wherein the monofunctional nucleophile is selectedfrom the group consisting of phenol, acetic acid and propanoic acid andthe catalyst is selected from the group consisting of a phosphonium orammonium salt.
 11. The process of claim 6 wherein the solvent isselected from the group consisting of 1-methyl-2-pyrrolidone,N,N-dimethylacetamide, water, diglyme, triglyme, diethylene glycol ethylether, diethylene glycol methyl ether, or propylene glycol methyl ether.12. A water-soluble polymer prepared by the process of claim
 6. 13. Acomposition comprising an aqueous fluid and the water-soluble polymer ofclaim
 1. 14. An aqueous solution comprising a polymer represented by theformula:

wherein each R is individually hydrogen or C₁-C₂₀ alkyl; R¹ is anaromatic or substituted aromatic moiety; Y is an organic moiety thatdoes not contain an epoxy group and Z is an organic moiety, optionallycontaining an epoxy group; x is 0-0.99; and n is 5-400; each A isindividually an amino group represented by one of the formulas:

wherein R² is hydrocarbyl or substituted hydrocarbyl; R³ is C₂-C₁₀hydrocarbylene or substituted hydrocarbylene; R⁴ is C₂-C₂₀hydrocarbylene or substituted hydrocarbylene; and each B is representedby the formula:

wherein R⁵ is hydrocarbyl; each R⁶ is individually hydrogen, methyl,ethyl, hydrocarbyl or mixtures thereof; and x is 0-0.99 when q isgreater than 40, but less than 0.2 or greater than 0.8 when q is lessthan
 40. 15. The aqueous solution of claim 14 wherein in the formularepresenting the polymer, R is hydrogen; each R¹ is individuallyisopropylidenediphenylene, 1,4-phenylene, 1,3-phenylene,methylenediphenylene, thidodiphenylene, carbonyldiphenylene, orcombinations thereof; each R² is individually methyl, ethyl, phenyl,benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl,2,3-dihydroxypropyl, 2-(acetamido)ethyl, or combinations thereof; R³ andR⁴ are individually ethylene, 1,2-propylene, 1,2-butylene, orcombinations thereof; and R⁵ is C₁-C₂₀ alkyl.
 16. The aqueous solutionof claim 14 wherein viscosity increases as temperature is increased. 17.A process which comprises dissolving the polymer of claim 1 in water,the water optionally containing acids, bases, salts, solvents, ormixtures thereof.